TWI388567B - Phosphorus containing compounds and the manufacturing method thereof - Google Patents

Description

Phosphorus-containing compound and preparation method thereof

The present invention relates to a phosphorus-containing compound and a process for the preparation thereof, and more particularly to a phosphorus-containing compound having high solubility and a process for the preparation thereof.

In order to cope with increasingly fine lines and high density, laminated boards are also required to have superior electrical properties, mechanical properties and heat-resistant workability. In particular, the heat-resistant workability, in the current common FR4 laminate, the glass transition temperature after hardening is about 130 ° C, for cutting and drilling processing in the printed circuit board process exceeding 200 ° C, even the welding procedure above 270 ° C Such laminate materials may be cracked or burst during manufacturing and processing. Therefore, development has been actively carried out for various laminate materials which emphasize high heat stability and high glass transition temperature. In addition, another important property for laminates is their flame retardant properties. In certain applications, such as aircraft, automobiles, and mass transit, vehicles pose a direct threat to human health and life. Therefore, the flame retardant characteristics of printed circuit boards are absolutely necessary.

In order to improve the flame retardant properties of laminate materials, certain materials with isolated flames to reduce combustion properties must be used. For laminates, it is customary to use halogen-containing compounds, especially bromine-containing epoxy resins and hardeners, and with flame retardant additives such as antimony trioxide to make the laminates flame retardant. Meet the required requirements (such as UL 94V-0 rating). In general, epoxy resins must contain up to 17% to 21% bromine content, combined with antimony trioxide or other flame retardants, to achieve UL 94V-0. However, The use of high bromine content epoxy resin or antimony trioxide will undoubtedly cause serious harm to humans. This is because antimony trioxide has been classified as a carcinogen; on the other hand, bromine is not burned. Only corrosive bromine radicals and hydrogen bromide are produced. The aromatic compounds with high bromine content can produce highly toxic brominated furans and brominated dioxins, which seriously affect the health and environment of the human body.

At present, phosphorus compounds have been widely studied and applied as a new generation of environmentally friendly flame retardants. For example, the phosphorus-containing compound disclosed in Taiwan Patent No. 575633 can form a difficult epoxy resin composition up to the level of UL 94V-0, and does not release corrosive and highly toxic gases during heating. . However, such a phosphorus-containing compound itself is hardly dissolved in a solvent generally used for an epoxy resin composition due to its structural relationship, and it can only be dissolved in a solvent having a relatively high polarity, so that a phosphorus-containing compound is to be applied. , it is bound to use a solvent with a higher polarity, so it is inconvenient for processing or application.

Therefore, there is still a need for a flame retardant additive which has high solubility, high cracking temperature and is suitable for use in thermosetting resins or thermoplastic trees.

The main object of the present invention is to provide a phosphorus-containing compound having high solubility and a process for producing the same.

Another object of the present invention is to provide a phosphorus-containing compound having a high cracking temperature and a process for the preparation thereof.

Still another object of the present invention is to provide a phosphorus-containing compound which can be used as a flame retardant additive and a process for producing the same.

To achieve the above and other objects, the present invention provides a phosphorus-containing compound having the structure of the formula (I): [wherein, the Ar is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen, a phenyl group substituted or unsubstituted naphthalene, anthracene, phenanthrene, anthrone, anthracene, biphenyl, diphenyl One of the group consisting of a trivalent group of diether, diphenyl sulfide, diphenylanthracene, di(phenyl)C1-6 alkyl, and di(naphthyl)C1-6 alkyl; Independent from the n system is an integer from 1 to 5]

The present invention further provides a method for producing a phosphorus-containing compound having the structure represented by the formula (I), which is obtained by reacting a compound represented by the formula (II) with an alkylene carbonate or an alkylene oxide, and then removing the solvent by heating. A phosphorus-containing compound having a structure represented by the formula (I).

Compared with the phosphorus-containing compound generally used as a flame retardant additive, the phosphorus-containing compound having the structure of the formula (I) of the present invention has not only the characteristics of high cracking temperature but also most of the organic solvents having high polarity and low polarity. It has excellent solubility and is suitable for use as a flame retardant additive for thermosetting or thermoplastic resins.

The phosphorus-containing compound of the present invention has a structure represented by the formula (I): Wherein, the Ar is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen group, a phenyl group substituted or unsubstituted naphthalene, anthracene, phenanthrene, anthrone, anthracene, biphenyl, diphenyl ether One of the groups consisting of diphenyl sulfide, diphenylsulfonium, di(phenyl)C1-6 alkyl, and di(naphthyl)C1-6 alkyl; m and n Independently an integer from 1 to 5. Preferably, the Ar is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a nitro group, a phenyl group substituted or unsubstituted biphenyl group, and a trivalent group of a di(phenyl) C1-6 alkyl group. One of the groups is formed; m and n are independently an integer of 1 to 3. More preferably, the Ar-based biphenyl trivalent group; m and n are independently an integer of 1 to 2.

In one embodiment, an alkyl group having from 1 to 6 carbon atoms includes, but is not limited to, methyl, ethyl, propyl, hexyl. Examples of halogens include from fluorine, chlorine, bromine, and iodine. Examples of the trivalent group of the di(phenyl)C1-6 alkyl group include di(phenyl)methyltriyl, di(phenyl)ethylenetriyl, di(phenyl)propanetriyl, and di(phenyl)hexyl. One of the trivalent base groups formed by the three bases. The trivalent group of the bis(naphthyl)C1-6 alkyl group is selected from the group consisting of di(naphthyl)methyltriyl, di(naphthyl)ethyltriyl, di(naphthyl)propyltriyl and di(naphthyl)hexyl. One of the groups consisting of the trivalent base of the three bases.

In the method of the present invention, (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl)-bis(4-hydroxyphenyl)methane (HPP) and carbonic acid are used. The alkene ester or alkylene oxide is reacted in a solvent under a heating condition of a catalyst, and then the solvent is removed to obtain a phosphorus-containing compound having a structure represented by the formula (I). Examples of the alkylene carbonate include, but are not limited to, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a halogen-substituted or unsubstituted ethylene carbonate or propylene carbonate. Esters such as fluoroethylene carbonate, chloroethylene carbonate, 5,5-diethyl-1,3-dioxopenta-2-one, and 5-methyl-5-propyl-1,3 - Dioxapentan-2-one and the like. In a preferred embodiment, ethylene carbonate is used, and the reaction formula is as follows:

The method of the present invention can also use (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl)-bis(4-hydroxyphenyl)methane (HPP) and epoxy. An alkane such as ethylene oxide is reacted in a solvent under a catalyst under heating, and then the solvent is removed to obtain a phosphorus-containing compound having a structure represented by the formula (I). The reaction formula is as follows:

On the other hand, the method of the present invention can also use (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl)-bis(4-hydroxyphenyl)methane (HPP). The phosphorus-containing compound having the structure represented by the formula (I) can be obtained by reacting with an alcohol compound in a solvent in which an acid scavenger is present, and then removing the solvent. The reaction formula is as follows: In the formula, X represents a halogen.

The process of the present invention is carried out under elevated temperature conditions, for example, in the range of from 100 to 210 ° C, preferably in the range of from 140 to 180 ° C, more preferably in the range of from 160 to 180 ° C. The solvent to be used in the method of the present invention is not particularly limited as long as it can dissolve the reactants and is easily removed, and N-methylpyrrolidone is preferably used.

The features of the present invention are further illustrated by the preferred embodiments, but are not intended to limit the scope of the invention.

Example Example 1

414.4 g of (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl)-bis(4-hydroxyphenyl)methane (HPP), 176.1 g of carbonic acid Vinyl ester (EC), 0.6 g of potassium iodide, and 1000 g of N-methylpyrrolidone were added to the reaction vessel, and the mixture was stirred and heated to 150 ° C to carry out a reaction for 8 hours until no carbon dioxide was produced in the reaction vessel. . After the reaction was completed, the solvent was removed by drying to obtain 468 g of a reaction product (HPPEC).

The composition of the elements was analyzed by ESCA, C: 68.5%, H: 5.2%, O: 20.33%, P: 5.97% (when m+n=2, theoretical value C: 69.32%, H: 5.42%, O: 19.10%, P: 6.16%). The FTIR analysis spectrum of the reactant HPP is shown in Fig. 1. The FTIR analysis spectrum of the product HPPEC is shown in Fig. 2; the second figure shows that the strong absorption peak at 2932 cm ^-1 indicates that -CH ₂ - is attached thereto. A strong absorption peak at 1251 cm ^-1 indicates that the hydroxyl group on the phenol has reacted to an ether group. The NMR spectrum of the product HPPEC is shown in Figure 3. The softening point of the resin was 95 °C.

Example 2

207.2 g of (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yloxy)-bis(4-hydroxyphenyl)methane, 45 g of ethylene oxide, 0.3 g of Potassium iodide and 500 g of N-methylpyrrolidone were added to the reaction vessel, and the mixture was stirred and heated to 150 ° C to carry out a reaction for 8 hours until no carbon dioxide was generated in the reaction vessel. After the reaction was completed, the solvent was removed by drying to obtain 230 g of a reaction product (HPPEO). The FTIR analysis of the product HPPEO is shown in Figure 4; Figure 4 shows that a strong absorption peak at 2930 cm ^-1 indicates that -CH ₂ - is attached to it, and a strong absorption peak at 1251 cm ^-1 indicates that the hydroxyl group on the phenol has been The reaction is an ether group. The softening point of the resin was 87 °C.

Test example 1

According to Table 1, 1 gram of the flame retardant additive HPP and 1 gram of the product HPPEC of Example 1 were dissolved in 20 gram of solvent, respectively, and the results are reported in Table 1.

×: indicates insoluble

◎: indicates easy to dissolve

○: indicates soluble

1 is an FTIR analysis chart of the reactant HPP of Example 1, FIG. 2 is an FTIR analysis chart of the product HPPEC of Example 1, and FIG. 3 is an NMR spectrum of the product HPPEC of Example 1; FTIR analysis of the product HPPEO of Example 2.

Claims (11)

a phosphorus-containing compound having the structure represented by formula (I), In the formula, the Ar is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen group, a phenyl group substituted or unsubstituted fluorene, phenanthrene, anthrone, anthracene, biphenyl, diphenyl ether, One of a group consisting of diphenyl sulfide, diphenylanthracene, di(phenyl)C1-6 alkyl, and a trivalent group of a di(naphthyl)C1-6 alkyl group; and m and n systems Independently an integer from 1 to 5. The compound of claim 1, wherein the Ar is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a nitro group, a phenyl group substituted or unsubstituted biphenyl group, and a di(phenyl) C1 group. One of the groups consisting of a trivalent group of -6 alkyl groups. The compound of claim 1, wherein the Ar-based biphenyl trivalent group. The compound of claim 1, wherein the halogen is one selected from the group consisting of fluorine, chlorine, bromine, and iodine. The compound of claim 1, wherein the alkyl group having 1 to 6 carbon atoms is one selected from the group consisting of methyl, ethyl, propyl and hexyl groups. The compound of claim 1, wherein the trivalent group of the di(phenyl)C1-6 alkyl group is selected from the group consisting of di(phenyl)methyltriyl and di(benzene). One of the trivalent group consisting of bis-triyl, di(phenyl)propanetriyl and di(phenyl)hexyltriyl. The compound of claim 1, wherein the trivalent group of the bis(naphthyl)C1-6 alkyl group is selected from the group consisting of di(naphthyl)methyltriyl, di(naphthyl)ethyltriyl, and One of the groups consisting of a trivalent group of a naphthyl)propyltriyl group and a di(naphthyl)hexyltriyl group. A method for producing a phosphorus-containing compound of the formula (I) as in the first aspect of the patent application, comprising: (a) a compound represented by the formula (II) under heating [wherein, the Ar is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a nitro group, a halogen group, a phenyl group substituted or unsubstituted fluorene, phenanthrene, anthrone, anthracene, biphenyl, diphenyl ether. One of the group consisting of diphenyl sulfide, diphenyl sulfonium, di(phenyl)C1-6 alkyl, and tris(naphthyl)C1-6 alkyl trivalent group] The ester or alkylene oxide is reacted in a solvent; and (b) dried to remove the solvent, and the product is recovered. The method of claim 8, wherein the alkylene carbonate is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or a halogen or no Substituted ethylene carbonate. The method of claim 8, wherein the alkylene carbonate It is selected from the group consisting of ethylene carbonate, propylene carbonate, vinyl fluorocarbonate, vinyl chlorocarbonate, 5,5-diethyl-1,3-dioxopenta-2-one, and 5-methyl- One of the groups consisting of 5-propyl-1,3-dioxopenta-2-one. The method of claim 8, wherein the alkylene oxide is ethylene oxide.